CN111004506B - Preparation method of modified cyanate ester resin with ultraviolet irradiation resistance - Google Patents
Preparation method of modified cyanate ester resin with ultraviolet irradiation resistance Download PDFInfo
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- CN111004506B CN111004506B CN201911337491.8A CN201911337491A CN111004506B CN 111004506 B CN111004506 B CN 111004506B CN 201911337491 A CN201911337491 A CN 201911337491A CN 111004506 B CN111004506 B CN 111004506B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a preparation method of modified cyanate ester resin with ultraviolet irradiation resistance, belonging to the technical field of preparation of high polymer materials. The invention solves the problem that the existing space ultraviolet radiation has damage effect on cyanate ester resin matrix. The invention utilizes the principle of POSS nano organic-inorganic hybrid material functionalization and interface tissue regulation and control to carry out TiO on POSS 2 The functional modification is carried out, so that the cyanate ester resin can be uniformly dispersed in a cyanate ester resin matrix, and the cyanate ester resin with the ultraviolet radiation resistance is prepared after curing. Due to the introduction of POSS, the surface of the material prepared by the invention can quickly form SiO when being irradiated by ultraviolet rays 2 The ceramic passivation layer can prevent the bottom cyanate ester matrix from being further corroded. And TiO in the material 2 When ultraviolet rays are irradiated, electrons in the valence band can absorb the ultraviolet rays and are excited to the conduction band, and hole-electron pairs are generated, so that the ultraviolet rays are absorbed to a certain extent.
Description
Technical Field
The invention relates to a preparation method of modified cyanate ester resin with ultraviolet radiation resistance, belonging to the technical field of preparation of high polymer materials.
Background
The cyanate ester resin has the characteristics of excellent dielectric property, mechanical property, low outgassing property and the like, and is more and more widely applied in the field of aerospace, such as a light shield of a satellite and a shipborne radome body of a radar radome. In the space environment, ultraviolet light irradiation is one of the most serious environmental factors influencing the normal operation of the spacecraft, and is easy to cause the degradation of the mechanical properties of the surface material of the spacecraft, thereby further influencing the normal operation of the spacecraft. Therefore, the modified cyanate ester resin with ultraviolet radiation resistance is provided, and is necessary to provide technical support for material selection of a new-generation high-performance composite material resin matrix of a spacecraft.
Disclosure of Invention
The invention provides a preparation method of cyanate ester resin with atomic oxygen irradiation resistance, aiming at solving the problem that space ultraviolet irradiation generates damage effect on cyanate ester resin matrix.
The technical scheme of the invention is as follows:
a preparation method of modified cyanate ester resin with ultraviolet radiation resistance characteristic comprises the following operation steps:
step one, taking absolute methanol as a solvent and concentrated hydrochloric acid as a catalyst, and carrying out hydrolytic condensation reaction on gamma-chloropropyltriethoxysilane at room temperature to prepare chlorine-modified cage octa-poly (gamma-chloropropyl) silsesquioxane, namely Cl-POSS;
dissolving 4-hydroxyphenyl diphenyl phosphate in N, N-dimethylformamide, sequentially adding Cl-POSS, triethylamine and KI into the solution, heating and stirring for reaction, filtering to remove the solvent after the reaction is finished, and sequentially using 0.1mol/L hydrochloric acid solution and deionized water for cleaning to obtain hydroxylated POSS (OH-POSS for short);
step three, dissolving tetrabutyl titanate in absolute ethyl alcohol, then adding the OH-POSS prepared in the step two, dropwise adding a mixed solution of acetic acid, distilled water and absolute ethyl alcohol after uniformly stirring, reacting at room temperature, and obtaining TiO after the reaction is finished 2 Functionalized POSS, abbreviated POSS-TiO 2 ；
Step four, heating cyanate ester resin at 100 ℃ to obtain yellow transparent liquid, and adding POSS-TiO 2 Stirring is continued at 100 DEG CStirring for 1h, removing bubbles in vacuum, and then curing in stages to obtain the cyanate ester resin with ultraviolet radiation resistance.
Further limiting, the specific operation process of the step one is as follows: adding gamma-chloropropyltriethoxysilane into a mixed solution of anhydrous methanol and concentrated hydrochloric acid, sealing and stirring at room temperature for reaction, washing with anhydrous methanol after the reaction is finished to obtain white powder, and dissolving the white powder in n-hexane or trichloromethane for recrystallization to obtain Cl-POSS.
More particularly, the volume ratio of the anhydrous methanol to the concentrated hydrochloric acid is 25.
Further limited, the reaction time is 24-36 h under sealed stirring at room temperature.
Further limiting, the feeding ratio of Cl-POSS, triethylamine and KI in the second step is 1g.
Further limiting, the reaction conditions of heating and stirring in the second step are as follows: keeping the temperature at 80 ℃ and reacting for 6-8 h.
Further defining, in the third step, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is 1:2, and the volume ratio of acetic acid, distilled water and absolute ethyl alcohol is 1.
And further limiting, the dropping speed of the mixed solution of acetic acid, distilled water and absolute ethyl alcohol is 10-20 drops/min in the third step, and the mixed solution reacts for 48-72 hours at room temperature after the dropping is finished.
Further limiting, the feeding ratio of OH-POSS, tetrabutyl titanate and acetic acid in the third step is 2g, 10mL.
Further limiting, POSS-TiO in the fourth step 2 The mass of (A) is POSS-TiO 2 And 1% -4% of the total mass of the cyanate ester resin, wherein the staged curing conditions are as follows: curing at 160 ℃ for 1.5h, then at 180 ℃ for 1.5h, then at 200 ℃ for 2h, and finally at 220 ℃ for 1h.
The invention has the following beneficial effects: the invention is based on the principle of POSS nano organic-inorganic hybrid material functionalization and interface tissue regulation and control, and TiO is carried out on the POSS nano organic-inorganic hybrid material 2 The functional modification is carried out, so that the cyanate ester resin can be uniformly dispersed in a cyanate ester resin matrix. The material prepared by the invention is prepared fromWhen POSS is introduced, siO is rapidly formed on the surface of POSS when the POSS is irradiated by ultraviolet rays 2 The passivation layer can prevent the cyanate ester substrate at the bottom layer from being further corroded, so that the ultraviolet radiation resistance of the cyanate ester resin is effectively improved. And nano TiO 2 When the ultraviolet light is irradiated, electrons on the valence band can absorb the ultraviolet light and are excited to the conduction band, and meanwhile, hole-electron pairs are generated, so that the ultraviolet light also has a certain absorption function. Therefore, the nano TiO-based material prepared by the invention 2 And the POSS nano hybrid material has the synergistic atomic oxygen irradiation resistance, and the ultraviolet irradiation resistance of the cyanate resin matrix is obviously improved.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified.
Embodiment mode 1:
adding gamma-chloropropyl triethoxysilane into a mixed solution of 500mL of anhydrous methanol and 20mL of concentrated hydrochloric acid, sealing and stirring at room temperature for reaction for 24h, washing with anhydrous methanol after the reaction is finished, and recrystallizing the collected white powder with n-hexane/trichloromethane to obtain cage octa (gamma-chloropropyl) silsesquioxane chloride (Cl-POSS).
Then, 0.6g of 4-hydroxyphenyl diphenyl phosphate was dissolved in 50mL of N, N-dimethylformamide, and after stirring for 10 minutes, 0.5g of Cl-POSS, 2mL of triethylamine and 0.2g of KI were added to the above solution in this order, and after the reaction was completed, the reaction was stirred at 80 ℃ for 6 hours, the solvent was removed, and then washed with 0.1mol/L hydrochloric acid solution and deionized water to obtain hydroxylated POSS (OH-POSS). Wherein the 4-hydroxyphenyl diphenyl phosphate is produced by Beijing Miruida technologies, inc.
Then dissolving 100mL tetrabutyl titanate in 200mL absolute ethyl alcohol, adding 10g OH-POSS into the dispersion after uniformly stirring, then dropwise adding a mixed solution of acetic acid, distilled water and absolute ethyl alcohol, wherein the mixed solution contains 5mL acetic acid, 10mL distilled water and 100mL absolute ethyl alcohol, stirring and reacting for 48h at room temperature to obtain POSS-TiO 2 。
Finally, the cyanate ester resin with certain quality is put at 100 DEG CHeating the mixture until the mixture is yellow transparent liquid, and adding POSS-TiO with the mass fraction of 4wt percent 2 Stirring at constant temperature of 100 ℃ for 1h, heating to 120 ℃ for 30min, carrying out vacuum defoaming treatment, then sequentially curing at 160 ℃ for 1.5h, curing at 180 ℃ for 1.5h, then curing at 200 ℃ for 2h, and finally curing at 220 ℃ for 1h to obtain the cyanate resin with ultraviolet irradiation resistance.
The modified cyanate ester resin with ultraviolet radiation resistance prepared in the embodiment 1 is obtained through experimental characterization, and the mass loss rate of the modified cyanate ester resin after undergoing ultraviolet radiation for 5000 Equivalent Solar Hours (ESH) under a 1000W ultrahigh pressure spherical mercury arc lamp is only 0.010wt%.
Claims (1)
1. A preparation method of modified cyanate ester resin with ultraviolet radiation resistance is characterized in that the method comprises the following operation steps:
step one, taking absolute methanol as a solvent and concentrated hydrochloric acid as a catalyst, and carrying out hydrolytic condensation reaction on gamma-chloropropyltriethoxysilane at room temperature to prepare chlorine-modified cage octa-poly (gamma-chloropropyl) silsesquioxane, namely Cl-POSS;
the specific operation process of the step one is as follows: adding gamma-chloropropyltriethoxysilane into a mixed solution of anhydrous methanol and concentrated hydrochloric acid, sealing and stirring at room temperature for reaction, washing with anhydrous methanol after the reaction is finished to obtain white powder, and dissolving the white powder in n-hexane or trichloromethane for recrystallization to obtain Cl-POSS;
the volume ratio of the anhydrous methanol to the concentrated hydrochloric acid is 25;
step two, dissolving 0.6g of bis (4-hydroxyphenyl) phenyl phosphate in 50mL of N, N-dimethylformamide, sequentially adding Cl-POSS, triethylamine and KI into the solution, heating and stirring at 80 ℃ for reaction for 6 hours, filtering to remove the solvent after the reaction is finished, and then sequentially using 0.1mol/L hydrochloric acid solution and deionized water for cleaning to obtain hydroxylated POSS (OH-POSS for short);
in the second step, the feeding ratio of Cl-POSS, triethylamine and KI is 0.5 g: 2 mL: 0.2 g;
step three, dissolving 100mL of tetrabutyl titanate inAdding 10g of OH-POSS prepared in the second step into 200mL of absolute ethyl alcohol, uniformly stirring, dropwise adding a mixed solution of acetic acid, distilled water and absolute ethyl alcohol, reacting at room temperature, and obtaining TiO after the reaction is finished 2 Functionalized POSS, abbreviated POSS-TiO 2 ；
The volume ratio of the acetic acid to the distilled water to the absolute ethyl alcohol is 5mL to 10mL to 100mL;
step four, heating cyanate ester resin at 100 ℃ to form yellow transparent liquid, and adding POSS-TiO 2 Continuously stirring 1h at 100 ℃, removing bubbles in vacuum, and then curing in stages to obtain cyanate resin with ultraviolet radiation resistance;
in the fourth step, POSS-TiO 2 The mass of is POSS-TiO 2 And 4% of the total mass of the cyanate ester resin;
the staged curing conditions are as follows: curing at 160 ℃ for 1.5h, then at 180 ℃ for 1.5h, then at 200 ℃ for 2h, and finally at 220 ℃ for 1 h;
the reaction time is 24h by sealing and stirring at room temperature;
and in the third step, the dropping speed of the mixed solution of acetic acid, distilled water and absolute ethyl alcohol is 10 to 20 drops/min, and the mixed solution reacts at room temperature for 48h after dropping.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7160941B2 (en) * | 2001-05-01 | 2007-01-09 | Pentron Clinical Technologies, Llc | Dental composite materials and method of manufacture thereof |
| CN101300289A (en) * | 2005-10-28 | 2008-11-05 | 陶氏环球技术公司 | Silsesquioxane-titania hybrid polymers |
| CN101974028A (en) * | 2010-09-28 | 2011-02-16 | 哈尔滨工业大学 | Method for preparing polyhedral oligomeric silsesquioxanes containing titanium phenyl |
| CN105218811A (en) * | 2015-09-18 | 2016-01-06 | 西北工业大学 | A kind of phosphorus-silicon flame retardant type cyanate ester resin and preparation method thereof |
| CN105238505A (en) * | 2015-10-27 | 2016-01-13 | 广东月福汽车用品有限公司 | Braking-system lubricating grease and preparation method thereof |
| CN107011651A (en) * | 2017-04-28 | 2017-08-04 | 湖南工业大学 | A kind of nano composite material of POSS/ nylon monomer-cast nylons 6 and its preparation method and application |
| CN107059409A (en) * | 2017-02-06 | 2017-08-18 | 陕西科技大学 | Environment-friendly type polysilsesquioxane nano hybridization super-hydrophobic coating material and preparation method thereof |
| CN108431639A (en) * | 2016-03-09 | 2018-08-21 | 株式会社Lg化学 | Anti-reflective film |
| CN108473791A (en) * | 2016-03-04 | 2018-08-31 | 株式会社Lg化学 | Anti-reflective film |
-
2019
- 2019-12-23 CN CN201911337491.8A patent/CN111004506B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7160941B2 (en) * | 2001-05-01 | 2007-01-09 | Pentron Clinical Technologies, Llc | Dental composite materials and method of manufacture thereof |
| CN101300289A (en) * | 2005-10-28 | 2008-11-05 | 陶氏环球技术公司 | Silsesquioxane-titania hybrid polymers |
| CN101974028A (en) * | 2010-09-28 | 2011-02-16 | 哈尔滨工业大学 | Method for preparing polyhedral oligomeric silsesquioxanes containing titanium phenyl |
| CN105218811A (en) * | 2015-09-18 | 2016-01-06 | 西北工业大学 | A kind of phosphorus-silicon flame retardant type cyanate ester resin and preparation method thereof |
| CN105238505A (en) * | 2015-10-27 | 2016-01-13 | 广东月福汽车用品有限公司 | Braking-system lubricating grease and preparation method thereof |
| CN108473791A (en) * | 2016-03-04 | 2018-08-31 | 株式会社Lg化学 | Anti-reflective film |
| CN108431639A (en) * | 2016-03-09 | 2018-08-21 | 株式会社Lg化学 | Anti-reflective film |
| CN107059409A (en) * | 2017-02-06 | 2017-08-18 | 陕西科技大学 | Environment-friendly type polysilsesquioxane nano hybridization super-hydrophobic coating material and preparation method thereof |
| CN107011651A (en) * | 2017-04-28 | 2017-08-04 | 湖南工业大学 | A kind of nano composite material of POSS/ nylon monomer-cast nylons 6 and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| 《POSS 改性氰酸酯树脂体系研究》;方亮;《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》;20120515(第05期);摘要、2.2.1-2.2.3节、3.1节、3.3.1节 * |
| 《Synthesis and characterization of poly(methyl silsesquioxane)–titania optical thin films》;Wen-Chang Chen等;《J. Mater. Chem.》;20021231;第12卷;摘要、实验部分 * |
| 《八氯丙基多面体低聚倍半硅氧烷的合成与表征》;余洋等;《化工新型材料》;20081231;第36卷(第1期);第37-36、73页 * |
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